Process for producing polymers

ABSTRACT

A process for preparation of a polymer product comprising the steps of 
     i) feeding an aqueous mixture comprising a monoethylenically unsaturated monomer or a mixture of monoethylenically unsaturated monomers into a first reactor device ( 2 ) through at least one inlet; 
     ii) partially polymerizing the monomer or monomers and transferring the polymerizing monomer or mixture of monomers from the inlet to an outlet ( 3 ) of the first reactor device ( 2 ) to provide a partially polymerized product; 
     iii) flowing the partially polymerized product out of the outlet ( 3 ), in which no more than 60% of the monomer or mixture of monomers has been polymerized in the partially polymerized product as it exits the outlet ( 3 ) of first reactor device ( 2 ), and transferring it to a further reactor device ( 5 ), in which the further reactor device ( 5 ) has an inlet and an outlet ( 6 );
 
iv) continuing the polymerization in the further reactor device ( 5 ) and removing the polymer product from the outlet ( 6 ) of the further reactor device ( 5 ),
 
characterized in that the first reactor device ( 2 ) comprises a positive displacement pump.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. Non-Provisional applicationSer. No. 14/425,432, which was filed on Mar. 3, 2015, now issued as U.S.Pat. No. 9,382,364 and which is a continuation application of a NationalStage of PCT/IB2013/058769, which was filed on Sep. 23, 2013.PCT/IB2013/058769 claims the benefit of priority to U.S. ProvisionalApplication No. 61/705,647, which was filed on Sep. 26, 2012. Thisapplication is based upon and claims the benefit of priority to EuropeanApplication No. 12186016.7, which was filed on Sep. 26, 2012.

The present invention refers to a process for preparing polymers and areactor apparatus.

GB 1,054,028 describes a process for the batch-wise preparation ofwater-soluble polymers, which comprises polymerizing a monomer in anaqueous medium to form a viscous solution comprising the polymer andsqueezing the viscous solution out of the reactor by using a close fitpartition. The reactor is either a vertical or horizontal tube. If it isa vertical tube it has a conically shaped bottom part. The disadvantageof this reactor is that it does not allow a continuous preparation ofpolymer.

EP 0 725 084 A1 describes a process for preparing polymers whichcomprises polymerizing monomers in an aqueous medium to form a gel-likemixture comprising the polymer and squeezing the gel-like mixture out ofthe bottom of the reactor by using inert gas. The reactor used for thepolymerization consists of a top part, which is a vertical tube, and abottom part, which is of conical shape.

The disadvantage of this reactor is that some monomer comes down theinner walls of the reactor as a solution in the aqueous medium and has amuch reduced time to polymerize thus allowing some unreacted monomer toleave the reactor together with the polymer. This causes operationalproblems. In addition, the obtained polymer is contaminated withunreacted monomer and the presence of larger amounts of unreactedmonomer can lead to further processing problems when granulating anddrying the polymer.

If a polymer of low unreacted monomer content is needed, the unreactedmonomer has to be removed in an additional step, for example bytreatment with further initiator. However, polymers containing a largeramount of initiator are prone to degradation over time and thus are notfavoured.

WO 2006/117292 set out to overcome this problem by conducting thepolymerisation process in a conical reactor which is either a verticalfully conical reactor or is made up of 2 to 5 connected vertical conicalparts, which are on top of one another. The process made significantadvances in overcoming the aforementioned problems. Unfortunately thisprocess is still sometimes prone to the problem of the polymer productbeing contaminated with unreacted monomer.

Therefore it is an objective of the present invention to provide aprocess for more consistently preparing a polymer with low residualunreacted monomer. Further, it would also be desirable to provide such aprocess which can be operated continuously.

Thus according to the present invention a process for preparation of apolymer product comprising the steps of

i) feeding an aqueous mixture comprising a monoethylenically unsaturatedmonomer or a mixture of monoethylenically unsaturated monomers into afirst reactor device (2) through at least one inlet;

ii) partially polymerising the monomer or monomers and transferring thepolymerising monomer or mixture of monomers from the inlet to an outlet(3) of the first reactor device (2) to provide a partially polymerisedproduct;

iii) flowing the partially polymerised product out of the outlet (3) ofthe first reactor device (2), in which no more than 60% of the monomeror mixture of monomers has been polymerised in the partially polymerisedproduct as it exits the outlet of first reactor device (2), andtransferring it to a further reactor device (5), in which the furtherreactor device (5) has an inlet and an outlet (6);iv) continuing the polymerisation in the further reactor device (5) andremoving the polymer product from the outlet (6) of the further reactordevice (5), characterised in thatthe first reactor device (2) comprises a positive displacement pump.

By positive displacement pump we mean a device which will propel thepolymerising monomer and partially polymerised product through the firstreactor device.

Such positive displacement pumps may be either a reciprocating type or arotary type.

Reciprocating pumps for instance involve the action of components movingback and forth within a chamber. Reciprocating pumps are generallydivided into two categories, the first comprising a diagram and thesecond involving a piston or plunger. Examples of diaphragm pumpsinclude either simplex and multiplex actions. Examples of piston orplunger pumps include power piston or plunger pumps which may be singleacting or double acting and include simplex, duplex, triplex, ormultiplex actions. Alternatively the piston or plunger pumps may bescheme double acting which tend to be either simplex for duplex.

Rotary pumps include multiple rotor pumps or single rotor pumps. Amultiple rotor, may be of the gear, lobe, circumferential piston orscrew types. Single rotor pumps may be of the vane, piston, progressingcavity or peristaltic types. Gear pumps include pumps that comprise twoor more impellers within a rotary pump casing. Typically the impellersin a gear pump may take the form of toothed gear wheels, of helicalgears or of lobed cams. Multiple rotor pumps may be of the gear, lobe orcircumferential piston types.

However, it is important that whichever type of pump is selected it iscapable of transferring the polymerising monomer and partiallypolymerised product along the first reactor device. Pumps which areincapable transferring both polymerising monomer and partiallypolymerised product in this way will not be considered to be positivedisplacement pumps in accordance with the present invention.

In accordance with the invention we also provide an apparatus forpreparation of a polymer product comprising

BRIEF DESCRIPTIONS OF THE FIGURES

i) a first reactor device (2); and

ii) a further reactor device (5) comprising an inlet and an outlet (6),

characterised in that

the first reactor device (2) comprises a positive displacement pump.

FIG. 1 shows the preferred arrangement where in the monomer reservoir(1) feeds the monomer solution through the first inlet of the firstreactor device (2), being a progressive cavity pump. Partiallypolymerised product (pre-polymer) exits the first reactor device throughthe pre-polymer discharge point (outlet) (3) where the viscosity isassessed (4) and enters the second reactor device (5) where thepolymerization continues to finally exist through the polymer dischargepoint (outlet) (6) and into the downstream operation (7).

FIG. 2 shows another preferred setup where in the positive displacementpump is a gear pump.

Preferably, the first reactor device comprises a rotor within a statorand a multiplicity of cavities formed between the rotor and the statorin which the monomer or mixture of monomers enters and within which itis transferred as partially polymerising monomer or monomers from theinlet to the outlet of the first reactor device. More preferably thefirst reactor device comprises or is a progressive cavity pump.

The inventors of the present invention discovered that by partiallypolymerising the monomer in a first reactor device and then introducingthe partially polymerised product into the top of a further reactordevice that the polymer product can be prepared more consistentlywithout contamination from unreacted monomer.

However, the inventors also found that special care has to be taken inpreparing the partially polymerised product. It was discovered thatwithout the special features of the first reactor device the partiallypolymerised product may contain unreacted monomer separated from thepartially polymerised product. Further, when running the process incontinuous mode it was also found that the monomer may even bypasspartially polymerised product. It was unexpectedly discovered that byemploying a first reactor device comprising a positive displacement pumpand preferably a device which comprises a rotor within a stator and amultiplicity of cavities between the rotor and the stator that a moreconsistent partially polymerised product can be obtained. Generally inthis process unreacted monomer would tend to be distributed throughoutthe partially polymerised product.

Suitably no more than 60% by weight of the monomer or mixture ofmonomers should have been polymerised in the partially polymerisedproduct as it exits the outlet at the first reactor device. If theconversion of the monomer or monomer mixture exceeds this level it willgenerally be more difficult to remove the partially polymerised productfrom the first reactor device and also may risk the formation ofblockages within the first reactor device or is outlet. Typically nomore than 50%, usually no more than 40%, and often no more than 20 or30% and normally no more than 15% of the monomer or mixture of monomersshould have been polymerised in the partially polymerised product as itexits the outlet. If insufficient conversion of the monomer or monomermixture to a polymeric species has occurred it may be difficult toensure that the polymer product is not contaminated with unreactedmonomer. Generally above 0.1% by weight of the monomer or mixture ofmonomers should have been polymerised in the partially polymerisedproduct. C Suitably, this should be at least 1.0% by weight and often atleast 2.0% by weight or even at least 3% by weight.

It is generally desirable to ensure that the partially polymerisedproduct exiting the first reactor device exhibits suitable flowcharacteristics in order to facilitate the transfer of the partiallypolymerised product to the further reactor device. Further, the flowcharacteristics of the partially polymerised product entering thefurther reactor device may also facilitate the flow of the polymerisingproduct inside the further reactor device. The partially polymerisedproduct enters the further reactor device suitably through an inlet at afirst end and continues to polymerise within the further reactor deviceand the polymer product is removed from an outlet suitably at the secondend of the further reactor device. Preferably, as the partiallypolymerised product continues to polymerise it moves within the furtherreactor device from the first end to the second end such that the layersof polymerising material should transfer within the further reactordevice without any significant mixing with layers of polymerisingmaterial.

Suitably the viscosity of the partially polymerised product which exitsthe first reactor device may be up to 50,000 or up to 30,000 mPas. Oftenthe viscosity may be below 20,000 mPas and typically no more than 10,000mPas. The viscosity suitably may be at least 100 mPas and usually atleast 250 mPas and frequently at least 500 mPas. A particularly suitablerange of viscosity has been found to be between 1000 and 5000 mPas. Theviscosity of the partially polymerised product is measured at whatevertemperature it exits the first reactor device. Generally the temperaturewill be between −5 and 100° C., typically between 5° C. and 30° C.Viscosity can be measured by a suitable viscosity measuring instrumentwhich can be mounted in line.

A suitable instrument includes the In-Line Viscometer from CambridgeViscosity Incorporated of Medford, Mass., USA. The general literaturedescribes in line this rheometry instruments, for instance “In LineUltrasonic Rheology by Pulsed Doppler”, David M Pfund et al, Ultrasonics44 (2006), e477-e482 and “Methodology for In-Line Rheology by UltrasoundDoppler Velocity Profiling and Pressure Difference Techniques”, ChemicalEngineering Science 62 (2007) 4277-4293. U.S. Pat. No. 5,059,914describes microwave device for the continuous measurement of theviscosity of a viscous medium.

The residence time of the polymerising monomer or mixture of monomersfrom the inlet to the outlet of the first reactor device will usually beat least 20 seconds and often at least 30 seconds. Generally theresidence time would not exceed 30 minutes and typically no more than 20minutes and often not more than 10 minutes. Desirably the residence timeshould be between 0, 5 and 10 minutes, especially between 1 and 8minutes.

Typically the first reactor device would comprise an inlet at one endand an outlet at the other end. The rotor and the stator may generallybe regarded as being analogous to the rotor and the stator of aprogressive cavity pump. Preferably, the first reactor device is aprogressive cavity pump. The rotor is typically of a rigid constructionsuitably being of an eccentric helix. Generally it will be constructedof a metal, for instance steel. The stator may generally form of aflexible material, for instance rubber or other elastic resinousmaterial, and desirably formed as a sleeve which fits the rotor in orderto create a multiplicity of cavities between the rotor and inner surfaceof the stator. The exact number of cavities is not important butgenerally there will be at least 2 cavities and usually at least 4cavities. In some cases it may be desirable for there to be as many as30 or more cavities but usually there would be no more than 20 cavities.

Suitably the rotor should fit within the stator in order to create aseal so as to prevent any significant seepage of monomer or polymerisingmaterial between the cavities. During the operation of the process therotor should be rotated such that the cavities progress from the inletend to the outlet end of the first reactor device. The monomer ormixture of monomers should be introduced into a cavity and the inlet endof the first reactor device. As the rotor rotates the cavity will movefrom the inlet end of the first reactor device to the outlet end. Withineach cavity the monomer or mixture of monomers will polymerise to formthe partially polymerised product. The inventors have found that thepolymerising monomers tend to progress through the first reactor devicewith essentially plug flow. By this we mean that there is substantiallyno transfer of polymerising monomers and partially polymerised productbetween the different cavities. By substantially we mean that the amountof transfer between cavities is generally below 0.5% by weight andusually below 0.1% by weight.

The rotor should suitably rotate at a speed of at least 0.25 rpm andtypically at least 0.5 rpm. The rotation speed may be as much as 50 rpmor more but is generally below 30 rpm and often below 20 rpm. Preferablythe rotation speed should be between 1 and 15 rpm.

The positive displacement pump may be powered by any suitable powersource, for instance by a motor or other device that will drive thepump. It is possible that the power source may be located at either endof the first reactor device. However, it is preferred that the powersource is located at the outlet end of the first reactor device. This isespecially the case when the positive displacement pump is a rotorwithin a stator and a multiplicity of cavities formed between the rotorand the stator, in particular a progressive cavity pump. Desirably thepower source, for instance motor, maybe in direct communication with therotor of pump and preferably located such that the rotor is driven fromthe outlet end of the first reactor device. The inventors have foundthat by driving the rotor from the other end of the first reactor devicethere is an improved transfer of the partially polymerised productthrough the first reactor device and also improved ability to force thepartially polymerised product through the outlet of the first reactordevice and into the further reactor device.

The further reactor device may be any suitable polymerisation unit whichallows monomer or partially polymerised product to enter through aninlet and allow polymerisation with a form a polymer product which wouldbe removed from an outlet.

It may be desirable for the further polymerisation device to be mountedsubstantially vertically. It may be desirable for the first end to bethe upper end of the further reactor device and the second end to be thelower end. In this case the partially polymerised product would enterthe further reactor device through the inlet at the upper end (firstend) and the polymer product to be removed from an outlet at the lowerend (second end) of the further reactor device. The partiallypolymerised product would continue to polymerise within the furtherreactor device as it descends within the further reactor device.

Alternatively, the inlet end may be mounted at the lower end (first end)of the further reactor device and the outlet end mounted and the upperend (second end) of the further reactor device. In this case thepartially polymerised product would enter the further reactor devicethrough the inlet at the lower end and the polymer product would beremoved from an outlet at the upper end of the further reactor device.The partially polymerised product would continue to polymerise withinthe further reactor device.

Suitably the further reactor device may be an upright column typereactor with an inlet, side walls and an outlet. The cross-section ofthe further reactor device may be circular, elliptical or any polygonalshape. The walls of the further reactor device may be essentiallyparallel, for instance forming a cylinder and therefore being of atubular construction. Alternatively the further reactor device may beconical or at least contain conical sections. Further, the furtherreactor device may comprise at least one tubular or at least one conicalsection or a combination of at least one tubular and at least oneconical sections.

Preferably, the further reactor device is either a vertical fullyconical reactor having an angle (a) between top diameter (d1) of thefurther reactor device and inner wall of the reactor is smaller than 90°but larger than 45° or is made up of 2 to 5 connected vertical fullyconical parts, which are on top of one another, each having an anglebetween top diameter of a part and inner wall of smaller than 90° butlarger than 45°.

Desirably, the further reactor device is a vertical fully conicalreactor having an angle (α) between top diameter (d1) of the reactor andinner wall of the reactor of smaller than 90° but larger than 45°.

Preferably, the angle is smaller than 90°, but larger than 60°. Morepreferably, the angle is smaller than 90°, but larger than 70°. Evenmore preferably, the angle is smaller than 90°, but larger than 80°.Most preferably, it is smaller than 87° and larger than 83°.

The ratio of top diameter (d1) to bottom diameter (d2) of the reactorcan be from 1.1/1 to 24/1. Preferably, it is from 2/1 to 10/1. Morepreferably, it is from 3/1 to 8/1. Most preferably, it is from 5/1 to6/1.

When the further reactor device is made up of 2 to 5 connected verticalfully conical parts, the vertical fully conical parts can be the same ordifferent. The ratio of top diameter to bottom diameter of one of thevertical conical parts can be from 1.1/1 to 24/1. Preferably, it is from1.1/1 to 10/1. More preferably, it is from 1.2/1 to 5/1. Mostpreferably, it is from 1.5/1 to 3/1.

The further reactor device can be made of any suitable material, forexample steel, mild steel, stainless steel or glass fibre reinforcedplastic. The inner wall of the reactor is coated with an anti-adhesivecoating such as polytetrafluoroethylene (PTFE), perfluoroalkoxycopolymer (PFA) or fluoro ethylene propylene (FEP). The reactor has atleast one gas inlet and at least one inlet for feeding the monomer andinitiator at the top of the reactor and at least one outlet at thebottom of the reactor to remove the polymer. The reactor can be sealedpressure-tight. The reactor can have a cooling/heating device and astirring device, but preferably the reactor has no such devices.

The partially polymerised product may enter the further reactor deviceat a speed that allows a residence time of about 2 to 6 hours. Theresidence time depends on the monomer used and can be adjusted by aperson skilled in the art.

Preferably, the polymerization is performed in the absence of oxygen andin the presence of an inert gas such as nitrogen. Preferably, the inertgas pressure during the polymerization is between 1 and 10 bar, morepreferably, between 1 and 5 bar, and most preferably, between 1 and 3bar. The temperature of the reaction mixture can increase up to 100 Cduring polymerization. Preferably, the temperature of the reactionmixture is between 85 and 95° C. during polymerization. The temperaturecan be controlled by a heating and cooling device, but it is preferablycontrolled by the amounts of monomer and initiator in the aqueous mediumfed into the top of the reactor. The polymerization yields a polymer,which forms a gel-like mixture in the aqueous medium. The resultingpolymer usually contains between 1 and 10⁸ monomer units and is eitherwater-soluble or water-insoluble. It can be water-swellable ornon-water-swellable.

As soon as the polymer forms a gel-like mixture at the bottom of thefurther reactor device, the bottom outlet can be opened and the reactionmixture can be squeezed out from the bottom of the reactor using inertgas such as nitrogen. Preferably, the inert gas pressure applied isbetween 1 and 10 bar, more preferably, between 1 and 5 bar, and mostpreferably, between 1 and 3 bar.

Preferably, the content of unreacted monomer in the polymer obtained isbelow 0.15% by weight based on the weight of the polymer. Morepreferably, it is below 0.1% by weight based on the weight of thepolymer. Most preferably, it is below 0.01% by weight based on theweight of the polymer.

The obtained gel-like mixture comprising the polymer can be granulatedand dried in a conventional granulating and drying apparatus to yieldpolymer having a water content of below 12% by weight.

The process can be performed in a batch or continuous mode. Preferably,it is performed in a continuous mode.

The polymer produced by the process can be used to flocculate solidparticulates in water to aid water purification in industries rangingfrom mining to sewage treatment, bind paper fibres during the papermanufacturing process and coagulate metal ore particulates to enhancemetal extraction.

Also part of the invention is the reactor, which is adopted for theprocess of the present invention. Details regarding the reactor areexplained above.

Also part of the invention is polymer produced by the process of thepresent invention.

The monoethylenically unsaturated monomers can be water-soluble orwater-insoluble monoethylenically unsaturated monomers. Themonoethylenically unsaturated monomers may be obtained by a chemicallycatalysed process, a biologically catalysed process or a biologicalprocess.

Water-soluble monoethylenically unsaturated monomers can be carboxylicacids of formula

or salts thereof, in which R¹, R² and R³ are the same or different andare hydrogen, C₁₋₂-alkyl, carboxy or C₁₋₂-alkyl substituted withcarboxy,

wherein R⁷, R⁸ and R⁹ are the same or different and are hydrogen orC₁₋₂-alkyl, E is C₂₋₅-alkylene, R⁴, R⁵ and R⁶ are the same or differentand are C₁₋₄-alkyl and X is a suitable anion,Amides of Formulae

wherein R⁷, R⁸, R⁹, E, R⁴, R⁵, R⁶ and X have the meaning as indicatedabove, R¹⁰ is hydrogen or methyl, L is C₂₋₅-alkylene, and M is asuitable cation, vinyl derivatives or diallylammonium derivatives.

Examples of carboxylic acids of formula I are acrylic acid, methacrylicacid, crotonic acid, itaconic acid, maleic acid and fumaric acid. Saltsthereof can be ammonium or alkali metal salts thereof. Examples ofalkali metals are sodium and potassium.

C₁₋₂-Alkyl can be methyl or ethyl. Examples of C₂₋₅-alkylene areethylene, trimethylene, propylene, 2-methylpropylene, tetramethylene,ethylethylene and pentamethylene. Examples of C₁₋₄-alkyl are methyl,ethyl, propyl, isopropyl and butyl, isobutyl, sec-butyl and tert-butyl.Examples of suitable anions are halogenide, sulfate andC₁₋₄-alkylsulfate. An example of C₁₋₄-alkylsulfate is methylsulfate.Examples of a halogenide are bromide and chloride. A preferredhalogenide is chloride. Examples of suitable cations are hydrogen,ammonium and alkali metal.

Examples of esters of formula II are dimethylaminoethylacrylate methylchloride quaternary salt, diethylaminoethylacrylate ethyl chloridequaternary salt and dimethylaminoethylmethacrylate methyl chloridequaternary salt.

Examples of amides of formulae III, IV or V are acrylamide,methacrylamide, crotonamide, dimethylaminoethylacrylamide methylchloride quaternary salt, diethylaminoethylacrylamide ethyl chloridequaternary salt, dimethylaminoethylmethacrylamide methyl chloridequaternary salt and 2-acrylamido-2-methypropane sulfonic acid.

Examples of vinyl derivatives are vinylphosphonic acid or vinylsulfonicacid and salts thereof, such as ammonium or alkali metal salts thereof,N-vinylformamide, N-vinylpyrrolidinone and 1-vinylimidazole. An exampleof a diallylammonium derivative is diallyldimethylammonium chloride.

Water-insoluble monoethylenically unsaturated monomers can be esters ofcarboxylic acids of formula I with a C₁₋₁₈-alkanol.

Examples of C₁₋₁₈-alkanols are methanol, ethanol, propanol, isopropanol,butanol, hexanol, 2-ethylhexanol and octadecanol.

Examples of water-insoluble monoethylenically unsaturated monomers aremethyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate,stearyl acrylate, methyl methacrylate and stearyl methacrylate.

Preferably the monoethylenically unsaturated monomers are water-soluble.

More preferred monoethylenically unsaturated monomers are water-solubleand are selected from the group consisting of

Carboxylic Acids of Formula

or salts thereof, in which R¹, R² and R³ are the same or different andare hydrogen or methyl, carboxy or methyl substituted with carboxy,Esters of Formula

wherein R⁷, R⁸ and R⁹ are the same or different and are hydrogen ormethyl, E is C₂₋₃-alkylene, R⁴, R⁵ and R⁶ are the same or different andare C₁₋₃-alkyl and X is a suitable anion,Amides of Formulae

wherein R⁷, R⁸, R⁹, E, R⁴, R⁵, R⁶ and X have the meaning as indicatedabove, R¹⁰ is hydrogen or methyl, L is Cm-alkylene, and M is a suitablecation.

Examples of C₂₋₃-alkylene are ethylene, trimethylene and propylene.Examples of C₁₋₃-alkyl are methyl, ethyl, propyl and isopropyl.

Even more preferred monoethylenically unsaturated monomers arewater-soluble and are selected from the group consisting of

Carboxylic Acids of Formula

or salts thereof, in which R¹ is hydrogen or methyl and R² and R³ areboth hydrogen,Esters of Formula

wherein R⁷ is hydrogen or methyl, and Wand R⁹ are both hydrogen, E isethylene, R⁴, R⁵ and R⁶ are the same or different and are C₁₋₂-alkyl,and X is halogenide, sulfate or C₁₋₄-alkylsulfate,Amides of Formulae

wherein R⁷, R⁸, R⁹, E, R⁴, R⁵ and R⁶ and X have the meaning as indicatedabove, R¹⁰ is hydrogen or methyl, L is C₂₋₅-alkylene, and M is hydrogen,ammonium or an alkali metal.

Most preferred monoethylenically unsaturated monomers are water-solubleand are selected from the group consisting of acrylic acid or saltsthereof, esters of formula

wherein R⁷, R⁸ and R⁹ are hydrogen, E is ethylene, R⁴, R⁵ and R⁶ are thesame or different and are C₁₋₂-alkyl, and X is chloride, sulfate orC₁₋₄-alkylsulfate,Acrylamide and Amides of Formula

wherein R⁷, R⁸, R⁹ have the meaning as indicated above, L isC₂₋₄-alkylene, R¹⁰ is hydrogen, and M is hydrogen, ammonium or an alkalimetal.

Examples of C₂₋₄-alkylene are ethylene, trimethylene, propylene,2-methylpropylene, tetramethylene and ethylethylene.

Even most preferred the monoethylenically unsaturated monomer iswater-soluble and is either acrylamide or a mixture of acrylamide withwater-soluble monoethylenically unsaturated monomer selected from thegroup consisting of acrylic acid or salts thereof, and esters of formula

wherein R⁷, R⁸ and R⁹ are hydrogen, E is ethylene, R⁴, R⁵ and R⁶ are thesame or different and are C₁₋₂-alkyl, and X is chloride, sulfate orC₁₋₄-alkylsulfate.

Preferably, the amount of acrylamide in the mixture of acrylamide withwater-soluble monomethylenically unsaturated monomer selected from thegroup consisting of acrylic acid or salts thereof, and esters of formula

wherein R⁷, R⁸ and R⁹ are hydrogen, E is ethylene, R⁴, R⁵ and R⁶ are thesame or different and are C₁₋₂-alkyl, and X is chloride, sulfate orC₁₋₄-alkylsulfate, is at least 30% by weight based on the weight of themonomer mixture.

When the monomer or mixture of monomers comprises acrylamide, theacrylamide may have been produced by a suitable process, for instance byhydrolysis of acrylonitrile. Typically this may be one of the knownchemically catalysed processes using inorganic catalysts such as Raneycopper. Preferably however, the acrylamide would have been preparedusing a biological or biologically catalysed process. Suitably this maybe achieved by contacting acrylonitrile with a nitrile hydratase enzyme,for example as documented in the patents and literature. Superiorpolyacrylamide products may be obtained by employing the process of thepresent invention to polymerise acrylamide, optionally in combinationwith other ethylenically unsaturated monomers, wherein acrylamide hasbeen obtained by a biological process. Such polyacrylamides wouldexhibit superior properties as flocculants for instance for watertreatment (including sewage sludge treatment), mining applications andas retention/drainage aids in the paper industry.

Depending on the monoethylenically unsaturated monomer or monomermixture used, the polymers produced by the process of the presentinvention can be anionic, cationic or non-ionic.

Any suitable initiator can be used. The initiator can be, for example, aperoxide, a persulfate, an azo compound, a sulfate, a redox couple ormixtures thereof.

Examples of peroxides are hydrogen peroxide, potassium peroxide,tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide andbenzoyl peroxide. Examples of persulfates are ammonium, sodium orpotassium persulfate. Examples of azo compounds are2,2-azobisisobutyronitrile, 4,4′-azobis(4-cyanovaleric acid) and2,2′-azobis(N,N-dimethyleneisobutyramidine) dihydrochloride,1,1′-azobis(cyclohexanecarbonitrile) and 2,2′-azobis(2-amidinopropane)dihydrochloride. Examples of sulfates are ferrous ammonium sulfate andammonium sulfate. Redox couples consist of an oxidizing agent and areducing agent. The oxidizing agent can be one of the above listedperoxides, persulfates, sulfates or azo compounds, or an alkali metalchlorate or bromate. Examples of alkali metals are given above. Examplesof reducing agents are ascorbic acid, glucose or ammonium or alkalimetal hydrogen sulfite, sulfite, thiosulfate or sulfide, or ferrousammonium sulfate.

Preferably, the initiator is a mixture of a redox couple with one ormore initiators selected from the group consisting of peroxides,persulfates and azo compounds.

More preferably, the initiator is a mixture of a redox couple, whereinthe oxidizing agent is selected from the group consisting of peroxidesand alkali metal bromates, and the reducing agent is selected from thegroup consisting of ammonium or alkali metal hydrogen sulfite, sulfite,thiosulfate or sulfide, or ferrous ammonium sulfate, with one or moreazo compound initiators.

Even more preferably, the initiator is a mixture of a redox couple,wherein the oxidizing agent is selected from the group consisting ofhydrogen peroxides and alkali metal bromates, and the reducing agent isan alkali metal hydrogen sulfite or sulfite, with one or more azocompound initiators.

Most preferably, the initiator is a mixture of a redox couple, whereinthe oxidizing agent is selected from the group consisting oftert-butylhydroperoxide and potassium bromate, and the reducing agent issodium sulfite, with one or more azo compound initiators selected fromthe group consisting of 2,2-azobisisobutyronitrile,4,4′-azobis(4-cyanovaleric acid) and 2,2′-azobis(N,N-dimethyleneisobutyramidine).

The aqueous mixture comprising the monoethylenically unsaturated monomeror monomer mixture and an initiator can be a solution, dispersion or asuspension of the monomers and the initiator in water or buffer.Preferably, it is a solution of the monomers and initiator in water.

The aqueous mixture comprising the monomers and initiator may alsocontain additives such as urea, sequesterant agents, organic acids,chain transfer reagents and cross-linking agents.

Examples of sequesterant agents are diethylenetriaminepentaacetic acid,penta sodium salt, and diethylenediaminetetraacetic acid, tetra sodiumsalt.

Examples of organic acids are adipic acid, citric acid, oxalic acid,tartaric acid, malic acid and benzoic acid.

Examples of chain transfer reagents are thioglycolic acid, sodiumhypophosphite, 2-mercaptoethanol, N-dodecyl mercaptan and tert-dodecylmercaptan.

Examples of cross-linking agents are polyethylenically unsaturatedmonomer such as N,N-monomethylenebisacrylamide, poly(ethylene glycol)diacrylate, tetra allyl ammonium chloride and di allyl phthalate.

Preferably, the aqueous medium also contains urea, a sequesterant agentand/or an organic acid. More preferably, the aqueous medium alsocontains urea, diethylenetriaminepentaacetic acid, penta sodium saltand/or an adipic acid.

If the polymer produced by the process of the present invention iscationic, the aqueous medium most preferably also containsdiethylenetriaminepentaacetic acid, penta sodium salt and adipic acid.If the polymer produced is anionic the aqueous medium most preferablyalso contains diethylenetriaminepentaacetic acid, penta sodium salt andurea. If the polymer produced is non-ionic, the aqueous medium mostpreferably also contains diethylenetriaminepentaacetic acid, pentasodium salt, urea and adipic acid.

Preferably, the amount of the monoethylenically unsaturated monomer ormonomer mixture in the aqueous mixture is between 5 and 60% by weightbased on the weight of the aqueous mixture fed into the top of thereactor. More preferably, it is 10 to 50% by weight based on the weightof the aqueous mixture. Even more preferably, it is 25 to 40% by weightbased on the weight of the aqueous mixture. Most preferably, it is 28 to35% by weight based on the weight of the aqueous mixture.

Initiation of polymerisation of the monomer or mixture of monomersintroduced into the first reactor device may be achieved by the use ofconventional polymerisation initiators, for instance free radicalinitiation systems, such as redox initiators and/or thermal initiators.Suitable initiators include peroxides, for instance t-butyl peroxides,azo compounds, for instance azobisisobutyronitrile; inorganic compounds,such as potassium persulphate and redox couples, such as ferrousammonium sulphate/ammonium persulphate. It may be desirable to includethe initiators into the monomer or monomers prior to the introductioninto the first reactor device. Alternatively, initiators may beintroduced directly into the monomer or monomers within the firstreactor device. In some situations it may be desirable to introduceinitiators into the monomer or monomers prior to entry into the firstreactor device and then add further initiators to the monomer ormonomers within the first reactor device.

Polymerisation may also be effected by photo chemical irradiationprocesses, such as ultraviolet irradiation or by ionising irradiationfrom a cobalt 60 source.

Preferably, the total amount of initiator in the aqueous mixture isbetween 0.001 to 5% by weight based on the weight of the monomer ormonomer mixture. More preferably, it is 0.005 to 2% by weight based onthe weight of the monomer or monomer mixture. Most preferably, it is0.05 to 1% by weight based on the weight of the monomer or monomermixture. If the initiator is an initiator mixture comprising a redoxcouple, the amount of oxidizing agent is preferably from 0.0001 to 1%,more preferably from 0.0002 to 0.01%, by weight based on the weight ofthe monomer, and the ratio of reducing agent to oxidizing agent is from3/1 to 1/4, preferably from 2.5/1 to 1/3.

Preferably the amount of additives is between 0.0001 to 20% by weightbased on the weight of the monomer. More preferably, it is from 0.001 to15% by weight based on the weight of the monomer.

It may be desirable that the aqueous mixture comprising monomer ormonomer mixture and the initiator are prepared by vigorously mixing anaqueous solution of the monomer or monomer mixture with an aqueoussolution of initiator before feeding the resulting solution to the inletof the reactor. Alternatively an aqueous solution of initiator can beintroduced into the aqueous solution of the monomer or monomer mixturewithin the first reactor device and for instance be mixed togethervigorously. Preferably, the aqueous solution of ethylenicallyunsaturated monomers is degassed before being mixed with the initiatorsolution.

Preferably, the aqueous mixture comprising the monomer or monomermixture and the initiator can be prepared by vigorously mixing anaqueous solution containing the monomer or monomer mixture, one or moreazo compound initiators and additives such as urea, organic acids orsequesterant agents with an aqueous solution containing a redox coupleinitiator and optionally additional azo compound initiator beforefeeding the resulting solution to the first reactor device or afterintroduction of the aqueous solution containing the monomer or monomermixture into the first reactor device.

Preferably, the aqueous mixture comprising the monomer and the initiatoris cooled below 25 C, before being fed into the first reactor device.More preferably, it is cooled to 10° C. Even more preferably, it iscooled to 0° C. Most preferably, it is cooled to −5° C.

The advantage of the process of the present invention is that thereactor apparatus can run continuously without significant pressurechanges producing polymer with a low content of unreacted monomer. Thus,the problems of previous processes, namely inconvenient control of thepressure during the reaction, contamination of the dryer with unreactedmonomer and post-treatment of the polymer to reduce the amount ofunreacted monomer, are avoided.

The polymer product produced according to this invention typically mayhave an intrinsic viscosity (IV) of at least 4 dl/g, for instance atleast 5 or 6 dl/g or even higher, for instance at least 10 dl/g or evenmore than 14 or 15 dl/g. The intrinsic viscosity may be as high as 30dl/g but is usually up to 25 or 26 dl/g, for instance up to 21 or 22dl/g.

Intrinsic viscosity of polymers may be determined by preparing anaqueous solution of the polymer (0.5-1% w/w) based on the active contentof the polymer. 2 g of this 0.5-1% polymer solution is diluted to 100 mlin a volumetric flask with 50 ml of 2M sodium chloride solution that isbuffered to pH 7.0 (using 1.56 g sodium dihydrogen phosphate and 32.26 gdisodium hydrogen phosphate per liter of deionised water) and the wholeis diluted to the 100 ml mark with deionised water. The intrinsicviscosity of the polymers is measured using a Number 1 suspended levelviscometer at 25° C. in 1M buffered salt solution. Intrinsic viscosityvalues stated are determined according to this method unless otherwisestated.

The weight average molecular weight of the polymer beads shouldgenerally be at least 1 million, for instance at least 2 million andoften at least 3 million, preferably at least 5 million. In some casesthe weight average molecular weight may be at least 7 million andsometimes at least 10 million. The weight average molecular weight maybe as high as 18 or 20 million, for instance as high as 25 million oreven as high as 30 million or higher. The molecular weight can bedetermined for example by static light scattering, small angle neutronscattering, x-ray scattering or sedimentation velocity.

The following examples are an illustration of the invention.

Example 1: Preparation of an Anionic Polymer in a Plunger-TypeReciprocating Pump as Pre-Reactor

An aqueous monomer solution is prepared in a 5 L glass jacketed vesselwherein the vessel is equipped with a nitrogen inlet to deoxygenate thesolution for 15 minutes. The aqueous monomer solution contains 2128 g ofa 50 wt.-% aqueous solution of acrylamide, 1232.43 g of sodium salt of2-propenoic acid, 1.5 g of2-(azo(1-cyano-1-methylethyl))-2-methylpropane nitrile, 1.5 g of4,4′-Azobis(4-cyanovaleric acid), 3 ppm of a 70 wt.-% aqueous solutionof 2-methylpropan-2-peroxol and 1150 g of demineralized water. Thesolution is cooled down to an approximate temperature of 0° C. Theplunger-type reciprocating pump consists of a cylindrical fluorinatedbody with a plunger that moves within the internal space. The aqueousdegassed solution is fed to the plunger pump from the top. The mixtureis then stirred and initiated and shortly after a conversion of 20 wt.-%measured with a Temperature probe, the plunger-type reciprocatingpre-reactor is moved 135° counterclockwise and the contents are pushedtowards a receiving vessel where the reaction continues untilcompletion. The plunger vessel has an internal diameter of 60 mm and alength of 250 mm. After full conversion, the polymer is converted intodry powder from which the unreacted monomer is analyzed using HPLC. Theunreacted monomer accounts to less than 0.10% by weight.

Example 2: Preparation of a Cationic Polymer in a Progressive CavityPump

A mixture of acrylamide, acrylic acid and acryloxy ethyltrimethylammonium chloride are mixed and degassed and subsequentlyinitiated through a mixture of 4,4′-Azobis(4-cyanovaleric acid),2,2′-Azobis(2-methylpropionamidine) dihydrochloride and potassiumbromate in a first reactor. The pre-polymerized mixture is subsequentlyconveyed to a second vessel located at the exit of the first reactor.The temperature at the outlet of the first reactor is 20° C. and entersthe second reactor at a viscosity of 2300 mPas, which is estimatedthrough a differential pressure measurement. The first part of thereaction takes place in a progressive cavity pump with 27 cavitiesrotating at a speed of 10 rpm and the rest of the polymerizationcontinues in a second vessel.

The residence time within the first reactor is 8 minutes and within thesecond reactor is 4 hours. Analyses from the pre-polymer state theunreacted monomer is below 0.10% by weight with respect from activepolymer, which suggests that the contamination of the product withunreacted monomer was avoided and post polymerization treatment wasrequired.

Example 3: Preparation of a Cationic Polymer in a Tubular Reactor

Acrylamide solution is mixed in with acrylic acid and acryloxy ethyltrimethylammonium chloride together with a mixture of4,4′-Azobis(4-cyanovaleric acid), 2,2′-Azobis(2-methylpropionamidine)dihydrochloride and potassium bromate and pumped using a gear pumpthrough a tubular reactor with an internal diameter of 6 mm and a lengthof 3.2 m. The mixture is degassed for 15 minutes and cooled down to −1°C. The polymerization starts thereafter at the exit of the gear pump andcontinues within the tubular reactor until it reaches a viscosity of1000 mPas. At this point, the polymerization continues in a secondvessel batch-wise. The temperature at the end of the tubular reactor is7° C. and at the end of the polymerization is 90° C.

Example 4: Preparation of an Anionic Polymer in a Progressive CavityPump

A mixture of an aqueous acrylamide solution is mixed with a solution ofthe sodium salt of 2-propenoic acid and is initiated with 2,2′Azobis(2-methylpropionitrile), 2,2-Azobis (4-cyanopentanoic acid) andter-butylhydroperoxide. At this point, the mixture is degassed for 15minutes and cooled down to −1° C. A progressive cavity pump with 12cavities is used to convey 48.6 kg of the polymerizing monomer mixtureevery second towards a second reaction vessel, wherein the rest of thereaction takes place. The polymer leaves the pump after a residence timeless than 1 minute at a temperature of 17° C. In this case, the analysesshowed that the unreacted monomer after the second vessel was less than0.10% wt., which is tested after comminuting the polymer into powderparticles.

The invention claimed is:
 1. A process for preparing a polymer product,the process comprising: i) feeding an aqueous mixture comprising amonoethylenically unsaturated monomer or a mixture of monoethylenicallyunsaturated monomers into a first reactor through at least one inlet,wherein the first reactor comprises a positive displacement pump; ii)partially polymerising the monomer or monomers and transferring, withthe positive displacement pump, the polymerising monomer or mixture ofmonomers from the inlet to an outlet of the first reactor; iii) flowingthe partially polymerised product out of the outlet, in which no morethan 60% by weight of the monomer or mixture of monomers has beenpolymerised in the partially polymerised product as it exits the outletof first reactor, and transferring it to a further reactor, in which thefurther reactor has a further reactor inlet and a further reactoroutlet; iv) continuing the polymerisation in the further reactor andremoving a polymer product from the outlet of the further reactor,wherein the one or more monoethylenically unsaturated monomers areselected from the group consisting of acrylamide, methacrylamide,N-vinyl pyrrolidone, 2-hydroxy ethyl acrylate, acrylic acid, a salt ofacrylic acid, methacrylic acid, a salt of methacrylic acid, itaconicacid, a salt of itaconic acid, maleic acid, a salt of maleic acid,2-acrylamido-2-propane sulphonic acid, a salt of 2-acrylamide-2-propanesulfonic acid, vinyl sulphonic acid, a salt of vinyl sulphonic acid,allyl sulphonic acid, a salt of allyl sulphonic acid, dimethyl aminoethyl acrylate, an acid salt of dimethyl amino ethyl acrylate, aquaternary ammonium salt of dimethyl amino ethyl acrylate, dimethylamino ethyl methacrylate, an acid salt of dimethyl amino ethylmethacrylate, a quaternary ammonium salt of dimethyl amino ethylmethacrylate, dimethyl amino propyl acrylamide, an acid salt of dimethylamino propyl acrylamide, a quaternary ammonium salt of dimethyl aminopropyl acrylamide, dimethyl amino propyl methacrylamide, an acid salt ofdimethyl amino propyl methacrylamide, a quaternary ammonium salt ofdimethyl amino propyl methacrylamide, and a combination thereof.
 2. Theprocess of claim 1, wherein the first reactor further comprises a rotorwithin a stator and a multiplicity of cavities formed between the rotorand the stator in which the monomer or mixture of monomers enters andwithin which it is transferred as partially polymerising monomer ormonomers from the inlet to the outlet of the first reactor.
 3. Theprocess of claim 1, wherein no more than 35% of the monomer or mixtureof monomers has been polymerised in the partially polymerised product asit exits the outlet of first reactor.
 4. The process of claim 1, whereina viscosity of the partially polymerised product as it exits the outletof the first reactor is no more than 50,000 mPas.
 5. The process ofclaim 1, wherein a residence time of the polymerising monomer or mixtureof monomers from the inlet to the outlet of the first reactor is between20 seconds and 10 minutes.
 6. The process of claim 2, wherein the rotorof the first reactor rotates at between 1 and 15 rpm.
 7. The process ofclaim 1, wherein the further reactor comprises at least one tubular orat least one conical section or a combination thereof.
 8. The process ofclaim 1, wherein the further reactor is either a vertical fully conicalreactor having an angle (α) between a top diameter (d1) of the furtherreactor and an inner wall of the reactor is smaller than 90° but largerthan 45°, or is made up of 2 to 5 connected vertical fully conicalparts, which are on top of one another, each having an angle between atop diameter of a part and an inner wall of smaller than 90° but largerthan 45°.
 9. The process of claim 1, wherein one or more of themonoethylenically unsaturated monomers have been prepared by achemically catalysed process, a biologically catalysed process or abiological process.
 10. The process of claim 9, wherein the aqueousmixture comprises an acrylamide prepared by a biological catalysedprocess or a biological process.
 11. The process of claim 1, whichoccurs in a continuous mode.
 12. The process of claim 1, wherein theaqueous mixture consists of the monoethylenically unsaturated monomer orthe mixture of monoethylenically unsaturated monomers, a polymerizingagent and, optionally, a solvent or suspending agent.
 13. The process ofclaim 1, wherein the positive displacement pump is the first reactor.14. The process of claim 1, wherein the aqueous mixture passes throughthe first reactor with plug flow.
 15. The process of claim 1, whereinthe positive displacement pump is a plunger-type reciprocating pump.